LU85338A1 - PROCESS AND PLANT FOR THE PRODUCTION OF AN ORGANIC SOLUTION OF AN ORGANIC BASE INSOLUBLE IN WATER - Google Patents

Description

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Process and installation for the production of an organic solution of an organic base insoluble in water

Case S.83 / 5 SOLVAY & Cie (Société Anonyme)

The present invention relates to a process and an installation for the production of organic solutions of organic bases insoluble in water, in particular organic nitrogenous bases • v such as amines for example, by decomposition of chloride of immiscible organic cations with water, using a basic agent.

A technique is known for the manufacture of sodium bicarbonate according to which an aqueous solution of sodium chloride and an organic solution of an amine insoluble in water are mixed, the resulting mixture is treated with a gas containing anhydride carbonic solution, then subjected to decantation to separate an aqueous suspension of sodium bicarbonate, which is collected, and an organic solution of amine hydrochloride (patent GB-A-1082436 (KAISER ALUMINUM & CHEMICAL CORPORATION), page 2 , 15 lines 105 to 125; Central Patents Index, Basic Abstracts Journal, Section E, Week T.49, Derwent Publication Ltd., London, abstract 78430T-E: patent application JP-A-7241237 (Israel Mining Inds.

Inst. Res. & Dev.)).

In the following description, the expression "amine technique" will designate this known technique for the manufacture of sodium bicarbonate.

A technique is also known for the production * of ammonia by decomposition of ammonium chloride, according to which an aqueous solution of ammonium chloride is mixed with an organic solution of an amine insoluble in water and an inert gas or carbon dioxide is circulated through the resulting mixture to evacuate the ammonia produced (Central Patents Index, Basic Abstracts Journal, Section E, Week E / 14,

Derwent Publication Ltd, London (Great Britain), abstract. 30 26992E / 14: patent application JP-A-57034020 (TOYO SODA MFG K.K.)).

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In the known techniques which have just been described, an organic solution of amine hydrochloride is collected as a by-product which it is desirable to treat in order to regenerate the amine. For this purpose, a process is carried out by which the organic solution of amine hydrochloride is mixed with a basic agent in an aqueous medium, generally an aqueous suspension of calcium or magnesium hydroxide, and a solution is collected separately. organic of the regenerated amine and an aqueous solution of calcium or magnesium chloride (GB-A-1082436 (KAISER 10 ALUMINUM & CHEMICAL CORPORATION), page 3, lines 5 to 9; Central Patents Index, Basic Abstracts Journal, Section E, Week T.49,

Derwent Publication Ltd, London, abstract 78430T-E: patent application JP-A-7241237 (Israël Mining Inds. Inst. Res. & Dev.)). In this known process, there is generally encountered the difficulty of ensuring efficient recovery of the organic solution containing the regenerated amine; the regeneration of the amine by means of an aqueous suspension of calcium hydroxide is in fact accompanied by the formation of a solid residue consisting, in large part, of calcium carbonate or other solid impurities which disturb separation of the aqueous and organic solutions and cause a significant loss of regenerated amine (patent application JP-A-55/109219 (Toyo Soda)).

The invention aims to remedy this drawback by providing a process which makes it possible to efficiently produce an organic solution of a base which is insoluble in water, by decomposition of the chloride of an Organic cation by a basic agent, without loss of the base to be produced.

. The invention relates for this purpose to a process for the production of an organic solution of an organic base insoluble in water, ~ 30 according to which water is mixed, an organic solution of chloride of an organic cation, immiscible with water, and a basic agent capable of decomposing the organic cation chloride to form the base, and the organic solution containing the base and an aqueous phase containing a solid residue are separated; according to the invention, to separate the organic solution containing the base, from phase i%

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-3- aqueous, they are subjected to decantation, and at least part of a slurry separating the organic solution and the decanted aqueous phase is withdrawn and recycled to the above-mentioned mixture.

In the process according to the invention, the base is, by definition, any organic reagent having a basic character sufficient to form an organic cation chloride with hydrogen chloride.

In the process according to the invention, the choice of the organic solvent used to form the organic solution of organic cation chloride is conditioned by the need for it also to dissolve the base to be produced, thereby forming an organic solution immiscible with the water and aqueous solutions. The choice of the nature and the quantity of organic solvent to be used is moreover conditioned by the need for it, with the base to be produced, to form an organic solution whose viscosity does not prevent effective decantation. For this purpose, an organic solvent is preferably chosen which, at working temperature, has a viscosity which does not exceed 3 centipoise and preferably 1.5 centipoise. Furthermore, for safety and ease of use considerations, preference is given to low-volatility organic solvents having a flash point above the working temperature. The choice of organic solvent can also be conditioned by the destination of the organic solution of the base to be produced. For example, when seeking to produce an organic amine solution for the manufacture of sodium bicarbonate by the amine technique described above, it is desirable to choose an organic solvent which, in addition to the properties mentioned above, has a - · high absorption speed of carbon dioxide at moderate temperature, generally less than 100 ° C and more particularly between 15 and 70 ° C.

An organic solvent is preferably used for which the organic solution containing the base to be produced has a specific gravity lower than that of the aqueous phase. Advantageously, a solvent is chosen such as the difference between the specific weight of the aqueous phase and that of the organic solution to be produced. »T is at least equal to 5% of the specific weight of said organic solution, and preferably greater than 30% of this specific weight.

For economic considerations, the process according to the invention is preferably carried out at low temperature, generally at a temperature below 60 ° C, preferably between 15 and 40 ° C. In the case where it is intended to produce a nitrogenous base, an amine for example, the organic solvent can be advantageously selected from hydrocarbons, in a quantity controlled so that the solution of chloride of organic cation contains approximately 25 to 75% by weight of organic cation chloride. Examples of organic solvents which can be used in the context of the invention are xylene, butylbenzenes, methylethylbenzenes and more especially white spirit and commercial solvents known under the brands ISOPAR (Esso) which is a mixture of isoparaf-15 fine, SOLVESSO (Esso) which is a mixture of aromatic compounds, SHELLSOL AB (Shell) which is a mixture of aromatic compounds and SHELLSOL K which is a mixture of aliphatic compounds.

The basic agent has the function of decomposing the organic cation chloride to produce the base. It must be chosen so that the products of its reaction with the organic cation chloride are the base to be produced and water-soluble compounds, insoluble in the organic solution of the base. Inorganic basic agents are preferably used, basic agents especially recommended being the oxides and hydroxides of alkaline earth metals, and more especially calcium oxide and hydroxide.

Water must be used in an amount at least sufficient to dissolve all of the above-mentioned water-soluble compounds, i i resulting from the reaction of the basic agent with sodium chloride! - 30 organic cation.

; The solid residue of the aqueous phase consists of | particles of solid matter, insoluble in water and the organic solution of the base to be produced. It is generally an inorganic material and may be a product of the reaction of the basic agent with the chloride of organic cation or, more generally,

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-5- consist of impurities in the basic agent, which are not soluble in the aqueous phase. In the case of a basic agent which is not soluble in water, for example calcium hydroxide, this solid residue may sometimes also comprise particles of basic agent which have not reacted with the organic cation chloride . In the case where the basic agent used is calcium hydroxide obtained by calcination of limestone in a lime kiln, the solid residue consists, principally, of calcium carbonate and non-soluble limestone impurities in water, usually sand and clays.

In the process according to the invention, the organic solution of organic cation chloride, the basic agent and the water are intimately mixed to react the basic agent and the organic cation chloride and release the base into organic solution in the solvent and the other reaction products in water. At the end of the reaction, a mixture formed by the organic solution of the base to be produced, the aqueous phase and the solid residue is collected. According to the invention, this mixture is subjected to decantation in order to separate the organic solution containing the base from the aqueous phase containing the above-mentioned water-soluble compounds and a sediment comprising part of the solid residue.

The term “decantation” is intended to denote both a separation of immiscible liquid phases by gravity and a separation of such phases by centrifugation.

The decantation can be carried out in any suitable device, known per se. After decantation, the organic solution containing the base and the aqueous phase are separated by a layer of mud; this consists of a mixture of aqueous phase and of organic solution having the appearance of an emulsion and containing particles of solid matter in suspension. These solid particles constitute a part of the aforementioned solid residue, which could not settle in the aqueous phase during decantation.

According to the invention, at least part of the sludge is drawn off and recycled to the mixture of water, basic agent and organic cation chloride solution.

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-βίε process according to the invention accommodates either discontinuous operation or continuous operation. In the case of discontinuous operation, defined weights of the organic solution of organic cation chloride, of water and of basic agent are mixed in a reaction chamber, the resulting reaction mixture is subjected to decantation, then collects the three superimposed phases separately, namely the organic solution containing the base, the aqueous phase containing a sediment and the mud situated between this organic solution and this aqueous phase and the mud is reintroduced into the reaction chamber, with new defined fractions of organic solution of organic cation chloride, water and basic agent.

In the case of continuous operation, a reaction chamber is fed continuously with the organic solution of organic cation chloride, water and the basic agent, mixed therein, transferred continuously. , the resulting mixture in a settling chamber, an organic solution containing the base to be produced, a slurry and an aqueous phase containing a sediment are continuously withdrawn therefrom and the sludge is recycled in the reaction chamber. In this preferred mode of operation of the process, the rate of withdrawal and recycling of the sludge is adjusted so as to keep the thickness of the latter substantially constant in the settling chamber. The choice of this thickness is not critical, its optimum value being condi-tioned by the constructive characteristics of the settling chamber so as to avoid entrainment of mud with the organic solution containing the base or with the aqueous phase.

In the process according to the invention, it has been observed that, all other conditions remaining equal, the thickness of the layer of mud 30 between the organic solution of the base to be produced and the aqueous phase during decantation is rapidly established at an approximately constant value for a substantially constant rate of withdrawal and recycling of the sludge.

In carrying out the process according to the invention, it is advantageous to use an amount of basic agent which does not exceed the amount necessary to decompose all of the chloride of organic cation. It has been observed that, all other things being equal, this embodiment of the method according to the invention facilitates obtaining a steady state. In this embodiment 5 of the process according to the invention, it is possible, for example, to use an amount of basic agent greater than 50% of the amount necessary to decompose all of the organic cation chloride, the values between 75 and 98% being preferred.

The invention applies, in general, to all organic bases which are insoluble in water and capable of forming, with hydrogen chloride, chlorides of organic cations insoluble in water; it advantageously applies to nitrogenous organic bases, for example to imines insoluble in water and their derivatives, to quaternary ammonium salts insoluble in water and to amines and amine derivatives insoluble in water. The process according to the invention is applicable equally to the manufacture of primary, secondary or tertiary amines.

It finds a particularly advantageous application for the manufacture of primary amines from organic solutions of hydrochloride of primary amines, and especially of primary alkylamines comprising from 18 to 24 carbon atoms, which find an advantageous use in the manufacture sodium bicarbonate by the amine technique described above. To this end, the process according to the invention can advantageously be combined with said amine technique, where it is then used to regenerate the organic solution of amine starting from the organic solution of hydrochloride i of separate amine. aqueous suspension of sodium bicarbonate.

In this application of the method according to the invention, it is advantageous to subject the organic solution of amine hydrochloride to a decarbonation treatment before treating it with the basic agent; this decarbonation treatment can be carried out, for example, by a circulation of a current of air or inert gas through / through the solution, or by placing under vacuum.

The invention also relates to an installation for carrying out the method according to the invention, said installation comprising: - a reaction chamber comprising a mixing member; means for admitting an organic chloride solution of an organic cation, a basic agent and water into the reaction chamber; - a pipe for withdrawing the reaction mixture from the reaction chamber; and a decantation chamber into which the abovementioned withdrawal conduit opens, the decantation chamber comprising separate conduits for the evacuation of the decanted phases and, in the zone of separation of these, a withdrawal member which communicates with the reaction chamber.

Special features and details of the invention will emerge from the following description of some embodiments of the invention, with reference to the accompanying drawings.

Figure 1 schematically shows a particular embodiment of the installation according to the invention.

FIG. 2 is a diagram of an installation for the manufacture of sodium bicarbonate by the amine technique, implementing an embodiment of the method according to the invention.

In these figures, the same reference notations designate identical elements.

The installation shown in FIG. 1 is used for the preparation of an organic solution of a water-insoluble amine by means of the process according to the invention. To this end, it comprises a reaction chamber 1 which is supplied, continuously, with an organic solution of amine hydrochloride. 2 and a mixture 3 of basic agent and water, for example an aqueous suspension of calcium hydroxide. A stirrer 4 ensures the homogenization of the reaction mixture in reaction chamber 1. In this chamber, the amine hydrochloride reacts with calcium hydroxide to form an amine which passes into organic solution and chlorure calcium chloride which passes into aqueous solution.

The installation further comprises a settling chamber 5, which is continuously supplied with a mixture 6 formed of the organic amine solution and the aqueous calcium chloride solution, coming from the reaction chamber. 1, this mixture 6 5 further containing particles of a solid residue in suspension, generally limestone. In the settling chamber 5, the mixture 6 settles to form a lower aqueous phase 7 and an upper organic phase 8, separated by a slurry 9. The upper organic phase 8 consists of the organic amine solution to be produced and the phase lower aqueous 7 is formed of an aqueous solution of calcium chloride and comprises a sediment consisting mainly of limestone. The sludge is formed from a suspension of solid matter particles, mainly limestone, in a mixture of organic amine solution and aqueous calcium chloride solution, having the appearance of an emulsion. As the settling chamber 5 is supplied with the mixture 6, the organic amine solution produced is drawn off by overflow at 11; simultaneously, the aqueous phase is continuously drawn off at 12, at the bottom of the reaction chamber 5.

The withdrawal rate of the aqueous phase 12 is adjusted to permanently maintain the sludge 9 at a constant level 26. For example, it suffices to place a throttle valve with variable opening on the duct 12, or to place the outlet orifice of the f | conduit 12 at a suitable level above level 26 of the aqueous phase 7, as shown diagrammatically in FIG. 1.

In accordance with the invention, a fraction "13" of the sludge 9 is continuously withdrawn and recycled, via a pump 14, into the reaction chamber 1. The liquid flows 2, 3, 11, 12 and 13 being kept constant, it is observed that the height of the layer 30 of mud 9 is established at an approximately constant value.

This height can be increased or decreased at will, by decreasing or increasing the flow rate of the fraction withdrawn 13.

FIG. 2 shows the general diagram of an installation for the manufacture of sodium bicarbonate by the amine technique described above, which incorporates an embodiment

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"-10- preferred method according to the invention. The installation comprises a crystallization chamber 14 which is continuously supplied with a substantially saturated aqueous solution of sodium chloride 15, an organic solution of primary amine 11 insoluble in the aqueous solution of sodium chloride and a gas containing carbon dioxide 16. The organic primary amine solution may for example be a solution at 50% by weight of the primary alkylamine known under the brand PRIMENE JMT (Rohm &

Haas) in xylene. The gas 16 is preferably an enriched gas 10 containing 60 to 80% by weight of carbon dioxide, obtained for example by mixing in adequate proportions a lime gas with a residual gas from the calcination of sodium bicarbonate into monocarbonate sodium. The amount of gas used must be sufficient to convert a substantial part of the sodium chloride to sodium bicarbonate. As a variant, the treatment in the crystallization chamber 14 can be preceded by partial carbonation of the mixture by means of a gas poor in carbon dioxide, such as a lime kiln gas.

Is withdrawn from the crystallization chamber 14, a liquid 17 consisting of a mixture of aqueous solution and organic solution and containing crystals of sodium bicarbonate in suspension.

This liquid 17 is transferred to a settling chamber 18, where an organic solution of amine hydrochloride 19 and an aqueous slurry 20 of sodium bicarbonate crystals are separated by gravity. The latter is sent to a wringing or filtration device 21, where sodium bicarbonate 22 and mother liquor 23 are collected separately. The latter can be resaturated with sodium chloride to reconstitute the aqueous solution of sodium chloride 15 of departure.

The organic solution of amine hydrochloride 19 is treated in accordance with the process according to the invention, in order to regenerate the organic solution of amine 11. To this end, it is first subjected to a decarbonation treatment, by circulating it against the direction of an ascending stream of air 24 in a vertical column 25. The organic decarbonated solution 2, collected from column 25 is then treated as described above with reference to the FIG. 1, to produce an organic amine solution 11 which is recycled in the crystallization chamber 14.

The advantage of the invention will appear from the examination of the results of the tests, the description of which will follow. In each of these tests, sodium bicarbonate was made by the amine technique described above with reference to FIG. 2. For this purpose, a solution of approximately 50% by weight of the amine PRIMENE JMT was used. (Rohm & Haas) in an aromatic organic solvent known under the trademark SHELLSOL AB (Shell); the hourly flow rate of the organic solution was approximately 178.2 1. To regenerate the amine, the organic solution of amine hydrochloride coming from the settling chamber 18 was decarbonated as described above, then treated in the reaction chamber 1 with 18 l / hour 15 of a milk of lime containing 148 g of calcium hydroxide per liter. The resulting mixture was homogenized and then transferred to the settling chamber 5, where it decanted by gravity to form a lower aqueous phase 7, consisting of an aqueous solution of calcium chloride, an upper organic phase 8, consisting of solution of the amine PRIMENE JMT regenerated in the solvent SHELLSOL AB and, between these two phases, a slurry 9 having the appearance of an emulsion containing particles of solid matter in suspension, of flaky appearance. It was further observed that a sediment layer was formed in the bottom of the settling chamber 5, which was found to be calcium carbonate.

"Example 1 (reference test)

During the course of the test, as described above, a rapid proliferation of the mud layer 9 was observed to the detriment of the organic phase 8. After four hours of operation, the entire area of the chamber decantation 5, reserved for the organic phase 8 was occupied by the mud 9. To allow the continuation of the test, it was necessary to permanently withdraw 45 1 of mud per hour, which was evacuated. The test had to be stopped after 12 hours of uninterrupted operation, the organic phase then being completely absorbed by the mud.

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Example ne2 (test according to the invention)

During the course of the test, the height of the layer of mud 9 was constantly maintained equal to approximately 20 cm, by continuously withdrawing a flow of mud of between 20 and 80 l / hour, which was recycled in reaction chamber 1. The operation of the installation remained stable throughout the duration of the test which was 34 hours.

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Claims (10)

1. Process for the production of an organic solution of an organic base insoluble in water, according to which water is mixed, an organic solution of chloride of an organic cation, immiscible with water, and a basic agent capable of decomposing the organic cation chloride to form the base, and separating the organic solution containing the base and an aqueous phase containing a solid residue, characterized in that, to separate the organic solution containing the base, the aqueous phase is subjected to decantation and in that at least part of a slurry separating the organic solution and the decanted aqueous phase is drawn off and recycled to the above-mentioned mixture. 2. Method according to claim 1, characterized in that * selects the base from organic nitrogen bases. 15 3 - Method according to claim 2, characterized in that the base is selected from amines. 4. Method according to claim 3, characterized in that the solvent for the organic solution of organic cation chloride is selected, so that the aqueous phase has a specific gravity 20 at least 30% greater than that of the solution organic base. 5. Method according to any one of claims 1 to 4, characterized in that the basic agent is selected from the basic compounds of alkaline earth metals. 25 6 - Process according to claim 5, characterized in that - * · water and the basic agent are used in the form of an aqueous suspension of calcium hydroxide. 7. Method according to any one of claims 1 to 6, characterized in that an amount of basic agent is used between 75 and 98% of the weight necessary to decompose the r ““ * · "" "" “Λ“ -14- 8. Method according to any one of claims 3 to 7, characterized in that an organic solution of residual amine hydrochloride from the manufacture of sodium bicarbonate is used by reaction of an aqueous solution of sodium chloride , 5 of a gas containing carbon dioxide and an amine in organic solution. 9. Method according to claim 8, characterized in that before treating the organic solution of amine hydrochloride with the basic agent, it is subjected to a decarbonation treatment. 10 10 - Installation for the production of an organic solution of a base insoluble in water, in accordance with the process according to any one of claims 1 to 9, characterized in that it comprises: * - a reaction chamber (1) comprising a mixing member (4); 15. means (2) (3) for the admission, into the reaction chamber, of an organic solution of chloride of an organic cation, of a basic agent and of water; - a pipe (6) for withdrawing the reaction mixture from the reaction chamber; and 20. a decantation chamber (5) into which the abovementioned withdrawal conduit opens (6), the decantation chamber comprising separate conduits (11) (12) for the evacuation of the decanted phases (7) (8) and , in the zone (9) for separating them, a withdrawal member (13) which communicates with the reaction chamber (13.